Hydrocarbon conversion



y z u U G. EGLOFF NM. QM. NJN NN HYDROCARBON CONVERSION Filed May 5l,1940 June 29, 1943.

Patented June 29, -1943 HYDROCARBON' CoNvERsIoN Gustav Egloi, Chicago,Ill., assignor to Universal Oil Products Company, Chicago, Ill., acorporation of Delaware Application May 31, 1940, Serial No. 338,167

4 Claims.

This invention relates to a process for convert- Ing hydrocarbon oilinto substantial yields of high antiknock gasoline and further improvingthe antiknock value o! hydrocarbon fractions boiling substantiallywithin the gasoline range.

More specically it relates to a process for producing high antiknockgasoline by contacting hydrocarbon distillates with powdered crackingcatalysts under conditions adequate to produce high yields of desirablemotor fuel.l The fractions contemplated for conversion include naphtha,kerosene, gas oil, wax distillate and the like, preferably `of petroleumorigin, although similar suitable stocks from other hydrocarbon sourcesmay likewise be employed.

In one specic embodiment the present invention comprises contactingnaphtha with a powdered catalytic agent under cracking conditions oitemperature and pressure, separately contacting a higher boilinghydrocarbon fraction containing substantially no gasoline with apowdered catalytic agent in a second step, combining the reactionproducts under conversion conditions of temperature and pressure,i'ractionating the reaction products, recovering gas and gasoline andrecycling a portion of the insuillciently converted oil boiling abovethe gasoline range. A part ot the process gases may also be recycled.

'I'he invention is further understood by reference to the accompanyingdrawing which is diagrammatic and should not' be construed as limitingit to the exact conditions of apparatus shown therein.

Naphtha charging stock which may be cracked or straight' run isintroduced through line I,

of approximatny coo-1200 F. The reaction A products pass through line 33containing valve I4 to fractionator 35. Gasoline and gas are recoveredthrough line 36 containing valve 31, condenser and valve 39 enteringreceiver 40. The

gasoline is removed through suitable stabilizers,

not shown, through line 4I and valve 42. AA portion of the process gasesmay be removed through line 43 and valve 44. Another portion of theprocess gases may be recycled through 1ine V45 containing valve 46, pump41 and valve 48, joining with line I and thus being passed lthrough coil5 for further conversion.v Alternatively the recycled process gases maybypass heaters 5 and 24 and pass directly to'heater I5. Higher boilingIractionator bottoms may be removed fromfrac- Vtionator 35 through line49 and valve 50. A part through line 49 and may be recovered therefrom`by suitable means and maybe regenerated for l further use. or in certaininstances may' be d iscarded. The catalytic agents employed in thepresent process may vary considerably 'and it is not es'- sential thatthe same catalyst be used in the various steps. The amount of catalystused is apand valve I3 to line I4 and valve I5 and thence to coil I6which is disposed in heater I1. In place ot coil II, a heated orunheated reaction chamber.

may be used. Although shown Aas a coil, this-may comprise any type ofreaction zone, such as a reactionv chamber. A gas oil charging stock isin` troduced through line I8, valve I9, pump 2li, valve 2|, line 22 and-valve'23 to coil 24 which is disposed in heater 25. A powdered crackingcatarst step for reforming the naphtha may comproximately 0.1-l0% andpreferably 0.5-5% by weight of oil. The catalytic agent used in theprise alumina, bauxite, magnesite, etc., or may comprise one or more ofthese materials, having deposited thereon promoting oxides of chro!mium, molybdenum, tungsten, vanadium, titanium, zinc oxide and the like.These agents are used as a ne powder, preferably of particle sizeapproaching colloidal dimensions. I

lyst is introduced from catalyst, charger 23 55 The catalytic agentemployed 11n the second step for cracking the higher boiling oil may coprise the so-called silica-alumina, silica-zirconia andsilica-alumina-zirconia catalysts which may. have added thereto minorportions of promoting compounds and particularly the oxides of elementssuch as chromium, molybdenum, vanadium, thorium, titanium andthe like,and which are preferably prepared by the separate or simultaneousprecipitation of the components under conditions such that nely dividedpowder l esults. This may then be followed by suit le washing and dryingsteps so that alkalil metal ions aresubstantially eliminated. It iswithin the scope of the invention to use naturally-occurring earths orclays which may or may not have been further activated by chemicaltreatment, for example, with strong mineral acids.

As an alternative, a suitable catalyst for the primary reforming stepcomprises a mixture vof the catalysts just mentioned with thosedescribed vabove in connection with the primary reforming step. Thus,for example, when bauxite or alumina is used in the primary step andsilica-alumina is used in the secondary step, the two catavlysts aremixed and recovered as a mixture. 'This mixed catalyst maybe reactivatedby treatment with an oxygen-containing gas whereby the carbonaceous andhydrocarbonaceous deposits are removed, and a portion of the regeneratedmaterial may be returned to the primary reforming step, being mixed withthe fresh reforming catalyst.

Since comparatively small quantities of catalytic agents are employedvand since these catalysts may be relatively inexpensive, it is notnecessary to completely recover them and in some instances they may bediscarded without further use. f

It should be borne in mind that vthe various catalytic materialsdescribed are not necessarily exactly equivalent in their action.

The following example is givengto illustrate the practicability andutility of.. the process, but should not be construed as ,limiting it tothe exact conditions or catalytic materials used therein. Y Y

A Pennsylvania naphtha having an octane number of approximately 30 maybe mixed with a powdered catalyst consisting essentially of a majorportion of alumina having deposited thereon a relatively minor portionof chromia and reformed at a temperature of approximately 1075 F. A gasoil charging stock may be mixed with a silica-alumina composite andconverted at a temperature of'approximately 1000 F. The reactionproducts are mixed and maybe treated at a temperature of approximately1050 F. and finally fractionated to recover gasoline and gas. portion of,the insuiilciently converted oil boiling above the gasoline range maybe returned to the gas oil cracking step. A portion of the' processgases may be returned to the naphtha reforming step. A yield ofapproximately 80% of 79 octane number gasoline, together with smallquantities of gas and higher boiling oil suitable for use as a fuel oil,may be recovered in this manner. I claim as my invention:

l. A process for the productionA of high antijknock gasoline, whichcomprises catalytically reforming a relatively light oil in the presenceof a powdered dehydrogenating catalyst, simultaneously therewithcatalytically cracking a heavier hydrocarbon oil in the presence of apowdered cracking catalyst which is diierent from the dehydrogenatingcatalyst, combining products of reaction from both conversion steps,subjecting the mixture to continued conversion in the presence of themixed dehydrogenating and cracking catalysts, and thereafter separatinggasoline from lower and higher boiling conversion products.

2. A process for the production of high antlknock gasoline, whichcomprises catalytically reforming a relatively light oil in the presenceof a powdered dehydrogenating catalyst, simultaneously therewithcatalytically cracking a heavier hydrocarbon oil in the presence of apowdered cracking catalyst comprising a siliceous material which isdifferent from the dehydrogenating catalyst, combining products ofreaction from both conversion steps, subjecting the mixture to continuedconversion in the presence of the mixed dehydrogenating and crackingcatalysts, fractionating resultant conversion products to separatefractionated vapors in the gasoline boiling range from higher boilingconversion products and returning at least a portion of said higherboiling conversion products to the second mentioned conversion step.

3. A process for the production of high anti; knock gasoline, whichcomprises catalytically reforming a relatively light oil in the presenceof a 'powdered dehydrogenating catalyst, simultaneously therewithcatalytically cracking a heavier hydrocarbon oil in the presence of apowdered cracking catalyst comprising a siliceous material which isdiierent from the dehydrogenatlng catalyst, combining products ofreaction from both conversion steps, subjecting the mixture to continuedconversion in the presence of the mixed dehydrogenating and crackingcatalysts, separating vaporous conversion products from nonvaporousliquid residue containing the mixed catalysts, fractionating saidvaporous conversion products to separate fractionated vapors in thegasoline boiling range from higher boiling conversion products andreturning said higher boiling conversion products to the secondmentioned conversion step.

4. A process for the production of high antiknock gasoline, whichcomprises catalytically reforming a, relatively light oil in thepresence of a powdered dehydrogenating catalyst, simultaneouslytherewith catalytically cracking a heavier hydrocarbon oil in thepresence of a powdered cracking catalyst comprising a siliceous materialwhich is different from the dehydrogenating catalyst, combining productsof reaction from both conversion steps, subjecting the mixture to con- Ytinued conversion in the presence of. the mixed dehydrogenating andcracking catalysts, separating vaporous conversion products fromnonvaporous liquid residue containing the mixed catalysts, fractionatingsaid vaporous conversion products to separate fractionated vapors in thegasoline boiling range from higherboillng conversion products.'returning said higher boiling conversion products to the secondmentioned conversion step, cooling and condensing said fractionatedvapors, collecting resultantl distillate and gas and returning at leasta portion of said gas to the 'rst and second mentioned conversion steps.

GUSTAV E GIDFF.

